1. Field of the Invention
This invention relates to the synthesis of organic phosphate-phosphonates.
Phosphite-phosphonates can be made by the reaction of phosphorus trichloride with symmetrically disubstituted ethylene oxide followed by reaction with an acylating agent, especially an aldehyde, phosphite-phosphonates can be oxidized to phosphate-phosphonates.
Another route to phosphate-phosphonates involves the condensation of two moles of a dialkyl phosphite with an acid chloride in the presence of a molar amount of an acid acceptor such as triethylamine.
Reaction of a phosphorohalidite with an aldehyde and a trivalent phosphorus ester also produces organic phosphate-phosphonates.
Rearrangement of 1-hydroxyalkylidenediphosphonate esters yields the related phosphate-phosphonate.
When vinyl acetate is caused to react with a dialkyl hydrogen phosphite, the appropriate phosphate-phosphonate can be produced.
2. Description of the Prior Art
In U.S. Pat. No. 3,676,532 granted July 11, 1972 Turley discloses a method for preparing alkyl phosphate-phosphonates by condensing dialkyl phosphites with aroyl halides using tertiary alkylamines as hydrohalogen acid acceptors.
In U.S. Pat. Nos. 3,042,701 granted July 3, 1962 and 3,014,956 granted Dec. 26, 1961 Birum discloses haloalkyl phosphate-phosphonates prepared by reacting a phosphorohalidite with an aldehyde and a phosphorus triester.
In U.S. Pat. Nos. 3,014,951 and 3,014,944 Birum discloses a large number of phosphite-phosphonates made by condensing substituted oxiranes with phosphorus trihalide and aldehydes or ketones. Phosphite-phosphonates can be converted to phosphate-phosphonates by the methods disclosed in Birum patents U.S. Pat. Nos. 3,042,701 and 3,014,956.
In U.S. Pat. Nos. 2,924,553 granted Feb. 9, 1960 and 2,900,296 granted Aug. 18, 1959 Baker and Saul disclose preparation of a dialkyl benzoylphosphonate from reaction of a substituted benzoyl with a trialkyl phosphite. A similar reaction is disclosed by Ernsberger in U.S. Pat. No. 2,491,920 granted Dec. 20, 1949.
The rearrangement of a tetraalkyl 1-hydroxyalkylidenediphosphonate to the related phosphate-phosphonate ester has been published by Fitch and Moedritzer, Abstr. 140th ACS Mtg, Chicago, 41Q, Sept. 3, 1961; J. Am. Chem. Soc. 84, 1876 (1962); by Pudovik et al., Dokl. Akad. Nauk SSSR 143, 875 (1962); ibid 153, 616 (1963); and by Nicholson and Vaughn, J. Org. Chem. 36, 3843 (1971).